Collapsing cavitation bubbles, chemical effects

The transient nature of the cavitation event precludes conventional measurement of the conditions generated during bubble collapse. Chemical reactions themselves, however, can be used to probe reaction conditions. The effective temperature realized by the collapse of clouds of cavitating bubbles can be determined by the use of competing unimolecular reactions whose rate dependencies on temperature have already been measured. The sonochemical ligand substitutions of volatile metal carbonyls were used as... 

The effects of ultrasonic irradiation on photochemical reactions have been also reported. In those papers, effects of cavitation were demonstrated. Cavitation means the process in which micro bubbles, which are formed within a liquid during the rarefaction cycle of the acoustic wave, undergo violent collapse during the compression cycle of the wave.5) The dissociation of water to radicals is an example of these effects. Since activated chemical species such as free radicals have high reactivity, chemical reactions proceed. In other words, this phenomenon is a chemical effect of ultrasonic waves. 

Chemat et al. [14] found the ]oint use of US and microwaves for the treatment of edible oils for the determination of copper to shorten the time taken by this step to about a half that was required in the classical procedure (heating in a Buchi digester) or with microwave assistance, nitric acid and hydrogen peroxide. However, they did not state the specific medium where the microwave-US-assisted method was implemented and assumed US to have mechanical effects only, even though they mentioned a cavitational effect. This is a very common mistake in working with US that is clarified in an extensive discussion by Chanon and Luche [15] of the division of sonochemistry applications into reactions which were the result of true and false effects. Essentially, these terms refer to real chemical effects induced by cavitation and those effects that can be ascribed to the mechanical impact of bubble collapse. The presence of one of these phenomena only has not been demonstrated in the work of Chemat et al. [14] — despite the illustrative figure in their article — so their ascribing the results to purely mechanical effects of US was unwarranted. 

Concerning chemical effects, US is known to increase the reactivity of some chemicals. The high temperature and pressure within a collapsing cavitation bubble produced by US irradiation causes the formation of free radicals and various other species. The primary chemical effects are therefore the promotion and acceleration of reactions involved in sample digestion. 

The effects of US on surviving cells may include structural changes and interactions with deoxyribonucleic acid (DNA) [83]. The biological effects observed in vitro include fragmentation of cell membranes caused by the collapse of cavitation bubbles, microstreaming near the boundary layer and formation of radicals, which promote chemical reactions leading to wall decomposition [84]. Carstensen et al. [85] found the extent of cell disruption to be inversely proportional to the cell concentration. 

TTHE ACTION OF ULTRASONIC WAVES IN LIQUIDS can induce or accelerate a wide variety of chemical reactions (1, 2) The chemical effects of ultrasound have been explained in terms of reactions occurring inside, at the interface, or at some distance away from cavitating gas bubbles. In the interior of a collapsing cavitation bubble, extreme but transient conditions exist. Temper-... 

During ultrasonic irradiation of aqueous solutions, OH radicals are produced from dissociation of water vapor upon collapse of cavitation bubbles. A fraction of these radicals that are initially formed in the gas phase diffuse into solution. Cavitation is a dynamic phenomenon, and the number and location of bursting bubbles at any time cannot be predicted a priori. Nevertheless, the time scale for bubble collapse and rebound is orders of magnitude smaller than the time scale for the macroscopic effects of sonication on chemicals (2) (i.e., nanoseconds to microseconds versus minutes to hours). Therefore, a simplified approach for modeling the liquid-phase chemistry resulting from sonication of a well-mixed solution is to view the OH input into the aqueous phase as continuous and uniform. The implicit assumption in this approach is that the kinetics of the aqueous-phase chemistry are not controlled by diffusion limitations of the substrates reacting with OH. 

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